DNV GL’s Common practices for the analysis of...

DNV GL © 23 January 2019 SAFER, SMARTER, GREENERDNV GL ©

Henk Top

23 January 2019

OIL & GAS

DNV GL’s Common practices for the analysis of Biogas

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Henk Top and Jeroen Ubels

NEN - Metrology for Biomethane

DNV GL © 23 January 2019

Introduction

▪ Specification of biogas in the Netherlands

▪ Composition and physical properties

▪ Hydrocarbon- and water dewpoint

▪ Halogenated hydrocarbons

▪ Silicon’s

▪ Sulphur components

▪ Odorant

▪ Other trace components

▪ Microbes and particulates

▪ Solids

▪ Mobile facilities

▪ Summary

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Specification local grids Netherlands (MR Gaskwaliteit 01-01-2019)

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Parameter Min Max Unit

Wobbe-index 43.46 44.41 MJ/Nm3

Hydrocarbons > C1 0 5 mole % (propane equivalents)

Natural gas condensates 0 80 mg/Nm3 @ –3 °C

Water dewpoint 0 -10 °C @ 8 bar(a)

Oxygen (O2) 0 0.5 mole %

Hydrogen (H2) 0 0.5 mole %

Carbon dioxide (CO2) 0 10.32 mole %

Carbon monoxide (CO) 0 2900 mg/Nm3

Chlorine (organic) 0 5 mg Cl/Nm3

Fluorine (organic) 0 5 mg F /Nm3

Silicon 0 0.1 mg Si/Nm3

Sulfur (anorganic) 0 5 mg S/Nm3

Sulfur (organic) 0 6 mg S/Nm3

THT (odorant) 10 40 mg THT/Nm3

Total Sulfur (before odorisation) 0 20 mg S/Nm3

Total Sulfur (after odorisation) 0 31 mg S/Nm3

Gas temperature 5 20 °C

Particulates > 5 μm 0 100 mg/Nm3

Pathogenic microbes 0 500 microbes/Nm3


Composition and physical properties (ISO 6974 and 6976)

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He, H2, O2, N2, CO2 and C1 – C8

▪ Gas analysis (ISO 6974, part 3), based on Gas Chromatography (GC).

▪ Gas analysis is used to determine the quantity and quality of natural gas. The results form the basis to determine the calorific value and other physical properties according to ISO 6976, table 3).

▪ ISO 17025:2005 accreditation (RvA, scope K103)


Hydrocarbon liquid content (1)

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Hydrocarbon liquid content is calculated, based on compositional data form an extended

hydrocarbon analysis according to ISO 6975 (extended hydrocarbon analysis).

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

-30 -28 -26 -24 -22 -20 -18 -16 -14 -12 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 14 16

Dru

k [b

ar(

g)]

Temperatuur [°C]

Dauwpunt

PHLC 5 mg/m3 (n)

PHLC 10 mg/m3 (n)

PHLC 25 mg/m3 (n)

PHLC 50 mg/m3 (n)

PHLC 75 mg/m3 (n)

PHLC 100 mg/m3 (n)

PHLC 150 mg/m3 (n)

PHLC 200 mg/m3 (n)

PHLC 250 mg/m3 (n)

Liquid drop-out curves


Hydrocarbon liquid content (2)

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Principle of Manual Method (ISO 6570, part 2)


Water dew point (on-line)

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Portable SpectraSensors SS1000 analyser

Measurement range 0 – 422 ppm

No calibration needed

Needs pressure to calculate dew point


Halogenated hydrocarbons (screening)

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Interscience ISQ GC/MS system

Column OV-1/DB1/CP Sil 5CB

MS and FID in parallel (relative RF’s)

scanning 20 – 400 amu

Scotty 104 calibration mixture, 39 components

Chromatogram of landfill gas


Silicon’s (1)

Siloxane Abrivation Formula Boilingpoint Mol mass Vapor pressure

(25 oC)

SIM Ion

Trimethylsilanol

Hexamethyldisiloxane

Octamethyltrisiloxane

Decamethyltetrasiloxane

Dodecamethylpentasiloxane

Hexamethylcyclotrisiloxane

Octamethylcyclotetrasiloxane

Decamethylcyclopentasiloxane

Dodecamethylcyclohexasiloxane

TMS

L2

L3

L4

L5

D3

D4

D5

D6

C3H10SiO

C6H18Si2O

C8H24Si3O2

C10H30Si4O3

C12H36Si5O4

C6H18Si3O3

C8H24Si4 O4

C10H30Si5O5

C12H36Si6O6

oC

100

100

153

194

230

134

175

210

245

g/mol

90.2

162.4

236.5

310.7

384.8

222.5

296.6

370.8

445.0

kPa

2.13

4.12

0.52

0.05

0.009

1.14

0.12

0.02

0.003

Amu

75

147

221

207

281

207

281

355

-

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Silicon’s (2)

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Chromatogram of 20 ppb siloxane mixture SIM-mode

Detection limit < 10 ppb, runtime 20 minutes

Stability of siloxanes in Tedlar sample bag


Sulfur

Determination of sulfur components according to ISO 19739

▪ Agilent 6890 with FPD

▪ Agilent 490 micro GC (TCD & DMD – Differential Mobility Detector)

▪ Interscience Compact GC with PFPD

▪ Interscience ISQ GC/MS in SIM mode

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New development: IMS - Ion Mobility Detector

Agilent 490 micro GC & GAS Dortmund IMS

module

Detection limit approximately 10 ppb, runtime

60 seconds (H2S and COS)


Odorant

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CP-Sil 19 CB, length 6 meter

14% cyanopropyl-phenyl86% dimethylpolysiloxane

C4H8S

Detection limit 4 – 5 mg/m3

THT


Other trace components

Biogas cannot contain components that will mask the smell

of odorant after odorisation. However some trace

components like ammonia, aldehydes, ketones and

terpenes can influence the sense of odor (Rhinology).

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Terpenes


Microbes and particulates

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Gas sample volume 100 litres

Sampling with 0.2 µm cellulose filter Ø 47mm

Analysis of bacteria and fungi based on RNA/DNA

with Quantitative Polymerase chain reaction (Q

PCR), outsourced to biolab

Particulate matter (PM) by amount (weight)


Solids (black powder)

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Scanning Electron Microscope (SEM)Energy-dispersive X-ray spectroscopy (EDS or EDX) CHNS-pyrolysisParticle size distribution


Mobile facilities

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Elster-Instromet Encal 3000Interscience Compact GCAgilent 490 PRO micro GC (2 & 4 channels)

Main components: H2, CH4, N2, O2, CO, CO2

Sulphur components: THT, H2S, COS and mercaptans

Others: Terpenes and C2 – C12 hydrocarbons

Water dew point (-100 - +20 oC) Michell, Easidew

Gas temperature and pressure

Data acquisition and remote access (4G network)


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